CN114054054B - Ternary visible light photocatalysis nano composite material and preparation method thereof - Google Patents
Ternary visible light photocatalysis nano composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114054054B CN114054054B CN202111495191.XA CN202111495191A CN114054054B CN 114054054 B CN114054054 B CN 114054054B CN 202111495191 A CN202111495191 A CN 202111495191A CN 114054054 B CN114054054 B CN 114054054B
- Authority
- CN
- China
- Prior art keywords
- visible light
- ternary
- graphene quantum
- doped graphene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 34
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 239000002096 quantum dot Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- NFEURUSKIHJCRP-UHFFFAOYSA-N 1,2,3-trinitropyrene Chemical compound C1=CC=C2C=CC3=C([N+]([O-])=O)C([N+](=O)[O-])=C([N+]([O-])=O)C4=CC=C1C2=C43 NFEURUSKIHJCRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 8
- 229940045105 silver iodide Drugs 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 4
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical group O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a ternary visible light photocatalysis nano composite material and a preparation method thereof, belonging to the technical field of functional materials, and comprising the following steps: s1, preparing phosphorus-doped graphene quantum dots, wherein pyrene and nitric acid are used as raw materials to prepare trinitropyrene; adding water into the trinitropyrene, adding a phosphorus source, adjusting the pH to 10-11, and carrying out hydrothermal reaction at 180 ℃ to prepare a phosphorus doped graphene quantum dot; s2, preparing an S1 phosphorus doped graphene quantum dot aqueous solution, mixing with titanium dioxide nano particles, silver nitrate and potassium iodide, filtering, and drying to prepare a ternary visible light photocatalytic nanocomposite; the prepared nano material is put into methyl orange solution, and under the irradiation of visible light, the catalytic efficiency can reach 99.35% within 10 minutes, and the nano material shows excellent catalytic performance.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a ternary visible light photocatalysis nanocomposite and a preparation method thereof.
Background
The pollution of organic dye water brings great hidden trouble to the health and life of people, and has become a serious challenge worldwide. Semiconductor photocatalysis is a very promising approach to solve this problem. In semiconductor multi-component photocatalysis, various refractory pollutants from the environment are decomposed under ultraviolet/visible light irradiation, titanium dioxide is the most potential one of the known photocatalysis semiconductor materials studied, and has the characteristics of stable performance, no toxicity, low cost and the like, and is widely applied to various fields since 1972 when being applied to water decomposition for the first time. However, drawbacks such as a wide band gap, high recombination rate of carriers, etc. limit their photocatalytic efficiency. The existing preparation method of the photocatalysis composite material with titanium dioxide as a main component only has the catalytic degradation effect on organic dye dirt in water under ultraviolet light, but has poor catalytic effect in a visible light wavelength region, has extremely low utilization rate on solar energy, and is difficult to realize large-scale commercial use.
Disclosure of Invention
In order to solve the technical problems, the invention provides a ternary visible light photocatalysis nano composite material and a preparation method thereof, titanium dioxide nano-scale particles, phosphorus doped graphene quantum dots and silver iodide are combined into the nano composite material by a simple method, the phosphorus doped graphene quantum dots are introduced into the surface of the titanium dioxide to improve the photosensitization of the titanium dioxide, and form P/N sections with the titanium dioxide to obviously improve the carrier transmission reduction and the photo-generated electron recombination, the silver iodide and the titanium dioxide are coupled to construct a heterojunction to form interface energy deviation between the semiconductor surfaces, the charge hole separation efficiency can be increased, and the silver iodide has strong absorption capacity on the visible light radiation absorption; the composite material can efficiently utilize sunlight to decompose different organic pollutants in water.
The invention is realized by the following technical scheme.
The first object of the invention is to provide a preparation method of ternary visible light photocatalysis nano composite material, comprising the following steps:
s1, preparation of phosphorus doped graphene quantum dots
Using pyrene and nitric acid as raw materials to prepare trinitropyrene; adding water into the trinitropyrene, adding a phosphorus source, adjusting the pH to 10-11, and carrying out hydrothermal reaction at 180 ℃ to prepare a phosphorus doped graphene quantum dot;
s2, preparing an S1 phosphorus doped graphene quantum dot aqueous solution, mixing with titanium dioxide nano particles, silver nitrate and potassium iodide, filtering, and drying to prepare the ternary visible light photocatalysis nano composite material.
Preferably, in S1, the ratio of pyrene to nitric acid is 1g:100mL.
Preferably, in S1, the trinitropyrene is prepared by heating, refluxing and stirring for 12 hours in a water bath at 80 ℃.
Preferably, in S1, the phosphorus source is disodium hydrogen phosphate dodecahydrate.
Preferably, in S1, trinitropyrene: water: the phosphorus source was obtained in an amount ratio of 1mg:1mL:0.03g.
Preferably, in S1, the time of the hydrothermal reaction is 6 hours.
Preferably, in S1, after the hydrothermal reaction is completed, the solution is dialyzed for 24 to 36 hours using a dialysis bag having a molecular weight cut-off of 3500Da, and then dried.
Preferably, in S2, the raw materials are smoothly added as follows: dispersing titanium dioxide nano particles in a phosphorus doped graphene quantum dot aqueous solution, adding silver nitrate, uniformly mixing, and dropwise adding a potassium iodide aqueous solution in the stirring process.
Preferably, in S2, the concentration of the phosphorus doped graphene quantum dot aqueous solution is 0.2mg/mL, and the titanium dioxide nano particles: phosphorus doped graphene quantum dot aqueous solution: silver nitrate: the dosage ratio of potassium iodide is 0.5g:500mL:0.097g:0.092g.
A second object of the present invention is to provide a ternary visible light photocatalytic nanocomposite prepared by the above preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the titanium dioxide nano-scale particles, the phosphorus doped graphene quantum dots and the silver iodide are combined into the nano composite material, and the titanium dioxide, the phosphorus doped graphene quantum dots and the silver iodide are successfully compounded into the ternary nano material by simply dissolving in water and stirring a suspension for adsorption during the synthesis of the nano composite material, so that the method does not use modes such as heating, and the cost is low and the operation is convenient.
(2) The prepared nano material is put into methyl orange solution, and under the irradiation of visible light, the catalytic efficiency can reach 99.35% within 10 minutes, and the nano material shows excellent catalytic performance.
Drawings
FIG. 1 is a TEM image of the P25/PCDs/AgI material prepared in example 1;
FIG. 2 is a HRTEM diagram of the P25/PCDs/AgI material prepared in example 1;
FIG. 3 is a FESEM image of the P25/PCDs/AgI material prepared in example 1;
FIG. 4 is an EDS diagram of the P25/PCDs/AgI material prepared in example 1;
FIG. 5 is an XPS spectrum of the P25/PCDs/AgI material prepared in example 1;
FIG. 6 is a graph showing the catalytic performance of the materials of example 1 and comparative examples 1 to 4 on methyl orange.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
A preparation method of a ternary visible light photocatalysis nano composite material comprises the following steps:
(1) After 1g of pyrene and 100ml of nitric acid are mixed, the mixture is heated in a water bath at 80 ℃ to reflux and stir for 12 hours, reactants are added into 500ml of purified water to be filtered, yellow solid which is trinitropyrene is obtained, 40mg of trinitropyrene is put into 40ml of water, 1.2g of disodium hydrogen phosphate dodecahydrate is added as a phosphorus source, sodium hydroxide is added to enable the pH value of the mixed solution to reach 10, the mixed solution is placed into a 100ml reaction kettle, and the mixed solution is heated for 6 hours at 180 ℃. After cooling, the solution was filtered and dialyzed for 24 hours using 3500Da dialysis bags, and the dialyzed solution was cooled and dried to obtain phosphorus doped graphene quantum dots (PCDs).
(2) Taking 0.5g of commercial grade titanium dioxide nano particles (P25), dispersing in 500ml of (0.2 mg/ml) phosphorus doped graphene quantum dot aqueous solution, rapidly magnetically stirring for 0.5h, putting 0.097g of silver nitrate into the mixed solution, rapidly magnetically stirring for one hour, then dissolving 0.092 potassium iodide into 20ml of water, dropwise adding into the mixed solution, dropwise adding the mixed solution while stirring to find that the color is obviously changed into yellow green, filtering at 60 ℃ and drying to obtain the novel ternary excellent visible light photocatalytic nanocomposite (P25/PCDs/AgI) (titanium dioxide, phosphorus doped graphene quantum dots and silver iodide).
Example 2
(1) After 1g of pyrene and 100ml of nitric acid are mixed, the mixture is heated in a water bath at 80 ℃ to reflux and stir for 12 hours, reactants are added into 500ml of purified water to be filtered, yellow solid which is trinitropyrene is obtained, 40mg of trinitropyrene is put into 40ml of water, 1.2g of disodium hydrogen phosphate dodecahydrate is added as a phosphorus source, sodium hydroxide is added to enable the pH value of the mixed solution to reach 11, the mixed solution is placed into a 100ml reaction kettle, and the mixed solution is heated for 6 hours at 180 ℃. And (3) cooling, filtering to obtain a solution, dialyzing the solution for 36 hours by using a 3500Da dialysis bag, and cooling and drying the dialyzed solution to obtain the phosphorus doped graphene quantum dot.
(2) Taking 0.5g of commercial grade titanium dioxide nano particles (P25), dispersing in 500ml of (0.2 mg/ml) phosphorus doped graphene quantum dot aqueous solution, rapidly magnetically stirring for 0.5h, putting 0.097g of silver nitrate into the mixed solution, rapidly magnetically stirring for one hour, then dissolving 0.092 potassium iodide into 20ml of water, dropwise adding into the mixed solution, dropwise adding the mixed solution while stirring to find that the color is obviously changed into yellow green, filtering at 60 ℃, and drying at the temperature to obtain the novel ternary excellent visible light photocatalytic nano composite material (titanium dioxide, phosphorus doped graphene quantum dots and silver iodide).
Comparative example 1
Dispersing titanium dioxide nano particles (P25) in 500ml (0.2 mg/ml) of the phosphorus doped graphene quantum dot aqueous solution prepared in the step (1) of the example 1, rapidly magnetically stirring for 0.5h, filtering, and drying at 60 ℃ to prepare the P25/PCDs material.
Comparative example 2
And (3) rapidly magnetically stirring the P25 and the pure graphene quantum dot aqueous solution dispersed in 500ml of 0.2mg/ml for 0.5h, filtering, and drying at 60 ℃ to obtain the P25/CDs material.
Comparative example 3
Dispersing P25 in 500ml of 0.2mg/ml pure graphene quantum dot aqueous solution, rapidly magnetically stirring for 0.5h, putting 0.097g of silver nitrate into the mixed solution, rapidly magnetically stirring for one hour, dissolving 0.092 potassium iodide into 20ml of water, dropwise adding into the mixed solution, filtering, and drying at 60 ℃ to obtain the P25/CDs/AgI material.
Comparative example 4
Titanium dioxide nanoparticles (P25).
The materials prepared in examples 1 and 2 have similar properties, and the materials prepared in example 1 are characterized first, in which fig. 1 is a TEM image of P25/PCDs/AgI material, fig. 2 is an HRTEM image of P25/PCDs/AgI material, and from fig. 2, three lattice spacings, a planar lattice spacing of 0.35nm corresponds to P25, a planar lattice spacing of 0.231nm corresponds to AgI, and a planar lattice spacing of 0.243 corresponds to PCDs, thus proving successful synthesis of the composite material; fig. 3 is a FESEM view of the material, as can be taken from fig. 1 and 3, with TEM and FESEM images of the material fitting each other to a high degree, which shows that the nanocomposite is almost composed of spherical particles, and particle agglomeration is observed due to the high growth of the nanocomposite. FIG. 4 is an EDS chart of a material, FIG. 5 is an XPS spectrum chart of a material, and it is clear from FIGS. 4 and 5 that the three-way catalyst sample contains C, P, ag, I, TI, O elements, illustrative PCDs, agI, TIO 2 A three-way photocatalyst with stable structure is constructed by physical adsorption.
The performance of the P25/PCDs/AgI prepared in example 1 was characterized by the following procedure with reference to comparative examples 1 to 4:
0.1g of the catalysts of example 1 and comparative examples 1 to 4, respectively, was put into a 10mg/L methyl orange solution and sonicated in the dark for one hour to reach adsorption equilibrium. Under 300w visible light, 5ml of the sample solution was filtered every five minutes to test the methyl orange concentration in the solution. Specific results are shown in FIG. 6, and the results of FIG. 6 show that the material prepared in example 1 has a catalytic efficiency of 99.35% in 10 minutes under irradiation of visible light, and shows excellent catalytic performance, compared with those of comparative examples 1 to 4.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (9)
1. The preparation method of the ternary visible light photocatalysis nano composite material is characterized by comprising the following steps of:
s1, preparation of phosphorus doped graphene quantum dots
Using pyrene and nitric acid as raw materials to prepare trinitropyrene; adding the trinitropyrene into water, adding a phosphorus source, adjusting the pH to 10-11, and carrying out hydrothermal reaction at 180 ℃ to prepare a phosphorus doped graphene quantum dot;
s2, dispersing titanium dioxide nano particles in a phosphorus doped graphene quantum dot aqueous solution, adding silver nitrate, uniformly mixing, dropwise adding a potassium iodide aqueous solution in the stirring process, filtering, and drying to prepare the ternary visible light photocatalytic nanocomposite compounded by titanium dioxide, phosphorus doped graphene quantum dots and silver iodide.
2. The method for preparing the ternary visible light photocatalytic nanocomposite according to claim 1, wherein in S1, the ratio of pyrene to nitric acid is 1g:100mL.
3. The method for preparing the ternary visible light photocatalytic nanocomposite according to claim 1, wherein in S1, the preparation of the trinitropyrene is performed by heating and refluxing in a water bath at 80 ℃ for 12 hours.
4. The method for preparing a ternary visible light photocatalytic nanocomposite according to claim 1, wherein in S1, the phosphorus source is disodium hydrogen phosphate dodecahydrate.
5. The method for preparing a ternary visible light photocatalytic nanocomposite material according to claim 1, wherein in S1, trinitropyrene: water: the phosphorus source dosage ratio was 1mg:1mL:0.03g.
6. The method for preparing a ternary visible light photocatalytic nanocomposite material according to claim 1, wherein in S1, the time of the hydrothermal reaction is 6 hours.
7. The method for preparing a ternary visible light photocatalytic nanocomposite according to claim 1, wherein in S1, after the completion of the hydrothermal reaction, the solution is dialyzed for 24 to 36 hours using a dialysis bag having a molecular weight cut-off of 3500Da, and then dried.
8. The preparation method of the ternary visible light photocatalytic nanocomposite according to claim 1, wherein in S2, the concentration of the phosphorus doped graphene quantum dot aqueous solution is 0.2mg/mL, and the titanium dioxide nanoparticles: phosphorus doped graphene quantum dot aqueous solution: silver nitrate: the dosage ratio of potassium iodide is 0.5g:500mL:0.097g:0.092g.
9. A ternary visible light photocatalytic nanocomposite prepared according to the preparation method of any one of claims 1 to 8.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111495191.XA CN114054054B (en) | 2021-12-08 | 2021-12-08 | Ternary visible light photocatalysis nano composite material and preparation method thereof |
NL2031042A NL2031042B1 (en) | 2021-12-08 | 2022-02-22 | Ternary visible light photocatalytic nanocomposite and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111495191.XA CN114054054B (en) | 2021-12-08 | 2021-12-08 | Ternary visible light photocatalysis nano composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114054054A CN114054054A (en) | 2022-02-18 |
CN114054054B true CN114054054B (en) | 2023-11-17 |
Family
ID=80228973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111495191.XA Active CN114054054B (en) | 2021-12-08 | 2021-12-08 | Ternary visible light photocatalysis nano composite material and preparation method thereof |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114054054B (en) |
NL (1) | NL2031042B1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
CN107511161A (en) * | 2017-08-29 | 2017-12-26 | 浙江理工大学 | A kind of phosphorus doping graphene quantum dot graphite phase carbon nitride p n knots photochemical catalyst and its preparation method and application |
CN109174141A (en) * | 2018-10-12 | 2019-01-11 | 宝鸡文理学院 | A kind of preparation method of composite Nano catalysis material |
CN110817850A (en) * | 2019-12-21 | 2020-02-21 | 桂林理工大学 | Nitrogen-phosphorus co-doped graphene quantum dot and preparation method thereof |
CN111437842A (en) * | 2020-03-31 | 2020-07-24 | 绍兴文理学院 | Preparation of composite catalyst and method for degrading heavy metal by using composite catalyst |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140116509A1 (en) * | 2012-10-30 | 2014-05-01 | Sean Andrew Vail | Solid-State Dye-Sensitized Solar Cell Using Oxidative Dopant |
CN105214635B (en) * | 2015-10-26 | 2019-03-05 | 上海理工大学 | A kind of composite photo-catalyst and its preparation method and application |
-
2021
- 2021-12-08 CN CN202111495191.XA patent/CN114054054B/en active Active
-
2022
- 2022-02-22 NL NL2031042A patent/NL2031042B1/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
CN107511161A (en) * | 2017-08-29 | 2017-12-26 | 浙江理工大学 | A kind of phosphorus doping graphene quantum dot graphite phase carbon nitride p n knots photochemical catalyst and its preparation method and application |
CN109174141A (en) * | 2018-10-12 | 2019-01-11 | 宝鸡文理学院 | A kind of preparation method of composite Nano catalysis material |
CN110817850A (en) * | 2019-12-21 | 2020-02-21 | 桂林理工大学 | Nitrogen-phosphorus co-doped graphene quantum dot and preparation method thereof |
CN111437842A (en) * | 2020-03-31 | 2020-07-24 | 绍兴文理学院 | Preparation of composite catalyst and method for degrading heavy metal by using composite catalyst |
Non-Patent Citations (3)
Title |
---|
"AgI负载纳米介孔TiO2的制备及其光降解性能";高瑞 等;《青岛科技大学学报(自然科学版)》;第第41卷卷(第第2期期);摘要、第30页第1节实验部分,第32页最后1段至第33页最后第1段,图6-7和表1 * |
"Phosphorus-doped graphene quantum dots loaded on TiO2 for enhanced photodegradation";Zengsheng Guo et al.;《Applied Surface Science》;第第526卷卷;摘要、第1页右栏第2段、第2页左栏第2.2节P-GQDs制备部分和第2.3节P-GQDs/TiO2光催化剂制备部分 * |
"Preparation of novel ternary TiO2 QDs/CDs/AgI nanocomposites with superior visible-light induced photocatalytic activity";Asma Shoja et al.;《Journal of Photochemistry & Photobiology A: Chemistry》;第第385卷卷;摘要,第1页右栏最后1段至第2页右栏最后1段,Scheme 1,第12-13页第4节结论部分 * |
Also Published As
Publication number | Publication date |
---|---|
CN114054054A (en) | 2022-02-18 |
NL2031042B1 (en) | 2023-11-10 |
NL2031042A (en) | 2022-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Cheng et al. | One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties | |
Sun et al. | Mesocrystals for photocatalysis: a comprehensive review on synthesis engineering and functional modifications | |
Ma et al. | Effective photoinduced charge separation and photocatalytic activity of hierarchical microsphere-like C60/BiOCl | |
CN103480399B (en) | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof | |
Zhang et al. | Facile hydrothermal synthesis and photocatalytic activity of rod-like nanosized silver tungstate | |
CN108246331B (en) | ZnS micron composite material modified by graphene nitrogen carbide quantum dots and preparation method and application thereof | |
Huang et al. | In-situ fabrication of novel BiOCl/Bi5O7I 2D/3D heterostructures with enhanced photocatalytic activity | |
CN108067267B (en) | Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof | |
CN107308929A (en) | A kind of preparation method of graphene nano titanium dioxide compound photochemical catalyst | |
CN110624594A (en) | Magnetic Fe3O4/ZnO/g-C3N4Composite photocatalyst and preparation method thereof | |
CN111036243A (en) | Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof | |
Zhang et al. | Enhanced visible-light photocatalytic H2 production of hierarchical g-C3N4 hexagon by one-step self-assembly strategy | |
CN111185204B (en) | Visible-light-driven photocatalyst, and preparation method and application thereof | |
Kang et al. | Preparation of Zn2GeO4 nanosheets with MIL-125 (Ti) hybrid photocatalyst for improved photodegradation of organic pollutants | |
Ren et al. | Decoration of CdMoO4 micron polyhedron with Pt nanoparticle and their enhanced photocatalytic performance in N2 fixation and water purification | |
CN110615470A (en) | One-dimensional metal-doped rutile titanium dioxide nanowire and preparation method thereof | |
CN114768841A (en) | Transition metal phosphide-modified oxygen-doped ZnIn2S4Polarized photocatalytic material and preparation method and application thereof | |
CN113493221B (en) | Molybdenum dioxide/titanium dioxide nanocomposite and preparation method and application thereof | |
CN113117661A (en) | Catalyst of graphene quantum dot doped titanium dioxide, preparation method and application thereof | |
CN110586060B (en) | Composite photocatalyst with oxidation-reduction performance and preparation method thereof | |
CN109967095B (en) | Full-crystal heterojunction photocatalytic material and preparation method and application thereof | |
CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
Shandilya et al. | An overview of synthesis and photocatalytic application of carbon quantum dots-based nanocomposites | |
CN114054054B (en) | Ternary visible light photocatalysis nano composite material and preparation method thereof | |
CN110801857A (en) | Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |